US4528010A - Process for producing optical glass product - Google Patents

Process for producing optical glass product Download PDF

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Publication number
US4528010A
US4528010A US06/584,968 US58496884A US4528010A US 4528010 A US4528010 A US 4528010A US 58496884 A US58496884 A US 58496884A US 4528010 A US4528010 A US 4528010A
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Prior art keywords
product
aqueous solution
silicate
solution
leached
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US06/584,968
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English (en)
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Takao Edahiro
Nobuo Inagaki
Shiro Kurosaki
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Nippon Telegraph and Telephone Corp
Sumitomo Electric Industries Ltd
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Nippon Telegraph and Telephone Corp
Sumitomo Electric Industries Ltd
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Assigned to NIPPON TELEGRAPH & TELEPHONE PUBLIC CORPORATION A JAPANESE COMPANY, SUMITOMO ELECTRIC INDUSTRIES, LTD., A JAPANESE COMPANY reassignment NIPPON TELEGRAPH & TELEPHONE PUBLIC CORPORATION A JAPANESE COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: EDAHIRO, TAKAO, INAGAKI, NOBUO, KUROSAKI, SHIRO
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Assigned to NIPPON TELEGRAPH & TELEPHONE CORPORATION reassignment NIPPON TELEGRAPH & TELEPHONE CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 07/12/1985 Assignors: NIPPON TELEGRAPH AND TELEPHONE PUBLIC CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/008—Other surface treatment of glass not in the form of fibres or filaments comprising a lixiviation step
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
    • C03B37/016—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by a liquid phase reaction process, e.g. through a gel phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/50—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with alkali metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/50—Doped silica-based glasses containing metals containing alkali metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/24—Wet processes, e.g. sol-gel process using alkali silicate solutions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/36—Gel impregnation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S65/00—Glass manufacturing
    • Y10S65/901—Liquid phase reaction process

Definitions

  • This invention relates to a process for producing an optical glass product that can be used as a lens in cameras, precision optical devices, and optoelectronic apparatuses, and which provides a three-dimensional distribution of refractive index within the lens. More particularly, this invention relates to rod lens having a refractive index that varies in a radial direction.
  • a graded rod lens having a refractive index that decrease parabolically from the center outward in a radial direction in becoming increasingly popular as an optical product for use in copiers, facsimile apparatus, and fiber optics.
  • Such rod lens is made of either glass or plastic, and some such products have been used on a commercial scale (see Nikkei Electronics, Aug. 20, 1979, pp. 64-74).
  • the Selfoc lens (“Selfoc" is a tradename of Japan Selfoc Co., Ltd.), produced from multicomponent glass by an ion exchange method, is well known.
  • the production of rod lens by the ion exchange method has an inherent limiting factor, viz., the velocity of diffusion of the modifier ion that changes the refractive index at temperatures that do not deform the glass.
  • a monovalent ion such as Tl, Cs, Rb, K, Na or Li can be used as the modifier ion, and furthermore to reduce the uneven distribution of refractive index is not easy.
  • a large difference in refractive index can only be achieved by using Tl, but Tl is so toxic that it is not easy to handle.
  • molecular stuffing A new method that relies on an entirely different principle, referred to as "molecular stuffing", and which is free from the above defects, has more recently been developed.
  • a porous glass preform is prepared by phase separation, leaching, and washing; CsNO 3 is solidified within the fine pores in the glass preform to provide a certain concentration gradient of CsNO 3 ; and then the pores are collapsed so as to provide a glass rod doped with Cs 2 O whose concentration decreases parabolically from the center outward.
  • OPI Japanese Patent Applications
  • the open micropores produced in the leaching step have a defective pore size distribution (i.e., an annual ring or eccentricity), and as a result the desired variation in the distribution of the Cs 2 O concentration (and therefore the desired distribution of refractive index) is not completely obtainable.
  • the maximum porosity of the resulting porous glass preform is 50%, and a higher porosity can not be achieved industrially, so a glass rod prepared by "stuffing" using a concentrated aqueous solution of CsNO 3 , solidifying the CsNO 3 , unstuffing (leaching) the CsNO 3 , resolidifying the CsNO 3 and collapsing the micropores has a difference between the minimum and maximum refractive index of about 3.0% at most. Therefore, a porous glass preform having open micropores of a uniform desired size distribution has been strongly desired.
  • porous glass can be produced by the so-called Vycor method, ("Vycol” is a trademark of Corning Glass Works), the zeolite method, the white carbon method, the colloidal silica method and the silica gel method.
  • Vycor method (“Vycol” is a trademark of Corning Glass Works)
  • zeolite method the zeolite method
  • white carbon method the white carbon method
  • colloidal silica method the silica gel method.
  • silica gel process There are two variations of the silica gel process: in one variation, a mixture of an aqueous solution of sodium silicate with an acid is stirred vigorously at low temperatures to form a silica hydrosol, which is gelled, given a predetermined form, and leached; in the other variation, a mixture of a solution of silicate salt with an organic compound causing the Cannizzaro reaction is stirred under slight heating to cause a mild reaction until a gel is formed, and after the gel is given a predetermined shape, the gel is leached.
  • One object of this invention is to provide a process for producing a lens material, and particularly a rod lens material, having a desired distribution of refractive index, and particularly providing a desired large difference between the minimum and maximum refractive indexes, by using a porous glass preform having open micropores of a uniform size distribution.
  • Another object of this invention is to provide an inexpensive lens material of a desired size.
  • the present invention provides a process for producing an optical glass product having a predetermined distribution of refractive index in the interior of the product, the process comprising the steps of:
  • the present invention also provides a process described above wherein the aqueous silicate solution prepared in the step (a) above contains a member selected from the group consisting of ammonium, lithium, sodium and potassium.
  • the present invention further provides a process described above wherein the acidic aqueous solution of the step (b) above contains a cation capable of being converted to an oxide.
  • the present invention provides a process described above wherein prior to drying according to the step (d) above, the product is soaked in an organic solvent such as ethanol or propanol.
  • FIG. 1 is a flow sheet for the production of a SiO 2 glass preform containing R 2 O wherein R is Cs, Rb or Tl.
  • FIG. 2 is a flow sheet for the production of an Al 2 O 3 --SiO 2 glass preform containing R 2 O.
  • This invention has for the first time been accomplished by stopping the regular change due to diffusion (or ion exchange) of a compound that is converted to a dopant, and which compound is leachable in a leaching step of the silica gel process that does not use the Cannizzaro reaction.
  • Tl 2 O, Cs 2 O Rb 2 O or the like as a dopant that provides great refractive index within the glass (that is, by using a starting solution of a silicate salt that also contains at least one of three solutions, viz., a thallium silicate solution, a cesium silicate solution, and a rubidium silicate solution), and by controlling the composition and temperature of the starting solution so as to distribute the dopant in such a manner that the velocity of diffusion (or ion exchange) and the solubility are controlled to provide a parabolic distribution of refractive index, a glass preform, e.g., a rod lens material, having the desired distribution of refractive index can be provided.
  • a glass preform e.g., a rod lens material
  • a true solution, collodial dispersion, or a suspension that contains at least one salt selected from the group consisting of cesium silicate, rubidium silicate, and thallium silicate, and which optionally contains either quaternary ammonium silicate or collodial silica and any one of the three salts selected from among lithium polysilicate, sodium silicate and potassium silicate is prepared.
  • the true solution, collodial dispersion, or suspension desirably contain from about 0.1 to about 0.6 mol/liter of Si, expressed as SiO 2 .
  • an aqueous solution of sodium silicate containing, e.g., 6.8 wt% Na 2 O--25 wt% SiO 2 --balance H 2 O; an aqueous solution of potassium silicate containing, e.g., 8.3 wt% K 2 O--20.8 wt% SiO 2 --balance H 2 O; an aqueous solution of lithium polysilicate containing e.g., 2.1 wt% Li 2 O--20 wt% SiO 2 --balance H 2 O; an aqueous solution of quaternary ammonium silicate containing, e.g., 9.9 wt% quaternary ammonium ion--45 wt% SiO 2 --balance H 2 O, an aqueous solution of colloidal silica containing, e.g., 40 wt% SiO 2 --balance H 2 O, an aqueous solution of rubidium silicate containing, e
  • the aqueous solution of alkali silicate thus prepared is added to a dilute acid with stirring.
  • Any acid can be used so long as it is acidic in nature in an aqueous solution, and examples of such acids are organic acids such as dilute acetic acid, inorganic acids such as dilute H 2 SO 4 and an aqueous solution of H 3 BO 3 , H 3 PO 4 or Al 2 (SO 4 ) 3 .
  • the first half of the aqueous alkali silicate solution is added slowly under vigorous stirring, and the second half is added in one portion.
  • the resulting mixture has a pH of about 4.4.
  • the mixture is then heated for a few minutes and left to stand until a gel results.
  • a gel of desired shape may be obtained by cutting or otherwise working the gel.
  • the same purpose is achieved by pouring the aqueous alkali silicate into a vessel of a predetermined shape containing a dilute acid (with stirring), or by forming a mixture of the aqueous alkali silicate and a dilute acid under stirring and immediately pouring the mixture into a vessel of a predetermined shape.
  • the mixture given a predetermined shape may be left to stand for, e.g., three days, to provide a completely gelled mixture.
  • the gel may optionally be washed with aqueous NH 4 OH to neutralize the residual dilute acid.
  • the gel is then leached with water, an alcohol, ketone, an organic acid, an inorganic acid or a mixture thereof at a temperature in the range of from room temperature to the boiling point of the solvent.
  • a solvent consiting of 1 to 5% NHO 3 and 95 to 99% C 2 H 5 OH, preferably 3 wt% HNO 3 and 97 wt% C 2 H 5 OH, or an aqueous 1M NH 4 NO 3 solution can be used.
  • the Tl + , Cs + or Rb + ion dissolves out of the gel.
  • the organic matter dissolves out more slowly.
  • a dopant such as Li 2 O, Na 2 O or K 2 O that does not greatly increase the refractive index is incorporated in such a manner that its concentration increases from the center outward.
  • the ion-exchanged gel is then slowly dried under vacuum, for example, by reducing the pressure from atmospheric pressure to about 1 mmHg over a period of more than about 24 hours.
  • the gel is passed through a cold low-solubilizing solution, such as PrOH (0° C.), to stop the migration of Tl + , Cs + , or Rb + , and is further dried.
  • the dried gel is gradually heated to remove the organic matter by oxidative combustion.
  • the gel is dried by evaporating the water, alcohol, or other solvents in the micro-pores by means of creating a vacuum slowly as described above, or slowly reducing the partial pressure of water vapor in which it is placed.
  • the dried gel is slowly heated in an oxygen atmosphere to evaporate or burn the organic compound, and then the gel is heated to a higher temperature (e.g., 900° to 1450° C.), at which the micropores collapse (due to high surface tension) to form a transparent glass product.
  • a higher temperature e.g., 900° to 1450° C.
  • the distribution of the concentration of ions such as Tl + , Cs + , and Rb + being removed is determind by parameters of the surrounding conditions or diffusion constant in a diffusion equation such as the shape of the gel (e.g., spherical, cylindrical or oval shape), the porosity, the pore size, the surrounding liquid and temperature conditions.
  • a gel to be leached having a desired shape can be produced by pouring a stirred mixture of aqueous silicate salt and dilute acid into a vessel or a predetermined shape, e.g., a cylindrical plastic vessel, and then letting the mixture gel in that vessel.
  • a gel of silica salt and dilute acid can be worked, for example, by drum grinding (or polishing) to provide a gel rod which is then leached.
  • a gel of desired shape can also be produced by casting, drawing, pressing, rolling, and other conventional machining techniques.
  • the aqueous solution of alkali metal silicate salt may also contain a silicate salt of Mg, Ca, Sr and Ba, in such an amount that they remain in solution and that the process conditions described above are met.
  • the surrounding liquid is preferably heated for a short period of time, but this is not a critical requirement.
  • the aqueous silicate solution may further contain a dispersed substance such as, for example, Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 C, SiC, Si 3 N 4 , U 2 O 5 , Cr 2 O 3 , Fe 2 O 3 , CoO, NiO, MnO or CuO, or a salt, oxide or other forms of compounds of Nd and Sm.
  • the particle size of the dispersed substance should not exceed 70 ⁇ , and its content should not exceed 70 wt%.
  • a glass preform obtained from a silicate solution containing a compound of Nd or Sm is suitable for use in a laser.
  • R 2 O Tl 2 O, Cs 2 O, Rb 2 O
  • 12 is diluting water
  • 13 is 3 liters of a diluted aqueous solution
  • 14 is a dilute acid prepared by dissolving 160 g of Al 2 (SO 4 ) 3 .18H 2
  • H 2 SO 4 15 is diluting water; 16 is 3 liters of a diluted acid; 17 is a step wherein 13 is added to 16 with stirring, with the first half of 13 being added slowly and the second half added in one portion to provide a pH of about 4.4; 18A is a step of slightly heating the mixture for a few minutes until it turns into a gel; 18B is a step of casting the mixture obtained in 17 into a vessel of a predetermined shape; steps 19A and 19B are alternatives to steps 18A and 18B, wherein 19A is a step of cutting the gel into a predetermined shape, and 19B is a step of slightly heating the casting for a few minutes; 20 is a step of leaving the resulting gel for three whole days and nights; 21 is a step of leaving the gel in 10 liters of 1% aqueous NH 4 OH for one day; 22 is a step of heating the dried gel in 12 to 15 liters of 10 % aqueous NH 4 Cl at 70° C.
  • a 30%-70% mixture of a solution of quaternary ammonium silicate, consisting of 10% NH 4 -45% SiO 2 --balance H 2 O and a solution of cesium silicate consisting of 12% Cs 2 O--20% SiO 2 --balance H 2 O was diluted with water 10 fold, and the resulting dilution was mixed with a 3% aqueous solution of H 2 SO 4 with stirring, and the mixture was poured into a cylindrical Teflon coated vessel 20 mm in diameter and 50 mm high. The vessel was left to stand at room temperature overnight and the casting was taken out of the vessel and leached with 1M NH 4 NO 3 containing 5 wt% (NH 4 ) 2 B 4 O 7 at 50° C. for 3 hours.
  • the leached casting was immediately soaked in PrOH at 0° C. and left to stand overnight. Thereafter, the casting was slowly dried under vacuum by reducing the pressure to 1 mmHg over a period.of 50 hours and then heated slowly.
  • a gas mixture of He (80%) and O 2 (20%) was charged into the reactor, and its supply was continued while the casting was heated first to 600° C. over a period of 18 hours, and then to 1100° C. over a period of 5 hours.
  • a transparent glass rod 10 mm in diameter was produced. The rod was drawn to a diameter of 2 mm and cut and ground into a rod lens whose length was 1/4 ⁇ (pitch).
  • a transparent glass rod 10 mm in size was produced as in Example 1 except that the solution of 1M NH 4 NO 3 containing (NH 4 ) 2 B 2 O 7 was replaced by a solution of 1M NH 4 NO 3 containing 30 wt% KNO 3 and that the vitrification temperature was 950° C.
  • a rod lens obtained by cutting and grinding the rod to a length of 1/4 ⁇ (pitch) had very good focusing ability.
  • the process of this invention for producing a rod lens material has the following advantages.
  • a large-size product of a desired shape can be produced by gelling a mixture of alkali silicate solution with dilute acid in a large vessel;
  • An in-expensive product can be produced from an economical material through fairly simple steps that are easy to control;
  • a gel is formed from a uniform mixture of silicate solution and dilute acid, so the phase separation is uniform throughout the gel, and fluctuations in the refractive index is small in every part of the gel;
  • the concentration of a dopant to provide a high refractive index can be decreased or the concentration of a dopant to provide low refractive index can be increased from the center outward, to thereby provide a product wherein the refractive index is decreased from the center outward following a predetermined curve.
  • a material for self-focusing rod lens can be produced;
  • a Nd- or Sm-doped glass preform suitable for use in a laser can be produced from a silicate solution containing a compound of Nd or Sm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)
  • Silicon Compounds (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
US06/584,968 1980-08-25 1984-02-29 Process for producing optical glass product Expired - Lifetime US4528010A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP55117524A JPS5742547A (en) 1980-08-25 1980-08-25 Preparation of optical glass part
JP55-117524 1980-08-25

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US06295965 Continuation 1981-08-25

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JP (1) JPS5742547A (ja)
CA (1) CA1158260A (ja)
DE (1) DE3133541C2 (ja)
GB (1) GB2084131B (ja)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640699A (en) * 1982-05-14 1987-02-03 Hoya Corporation Process for producing glass product having gradient of refractive index
EP0215603A1 (en) * 1985-09-11 1987-03-25 AT&T Corp. Fabrication of high-silica glass article
US4765818A (en) * 1987-02-24 1988-08-23 Hoechst Celanese Corporation Porous glass monoliths
US4767435A (en) * 1984-02-14 1988-08-30 Hoya Corporation Process for producing transparent glass product having refractive index gradient
US4816049A (en) * 1985-07-12 1989-03-28 Hoya Corporation Process of surface treating laser glass
US4872895A (en) * 1986-12-11 1989-10-10 American Telephone And Telegraph Company, At&T Bell Laboratories Method for fabricating articles which include high silica glass bodies
US4898755A (en) * 1987-04-17 1990-02-06 Hoechst Celanese Corporation Inorganic-organic composite compositions exhibiting nonlinear optical response
EP0359588A2 (en) * 1988-09-16 1990-03-21 Hoechst Celanese Corporation Dye lasers
US4944986A (en) * 1988-09-23 1990-07-31 Zuel Company Anti-reflective glass surface
US5100841A (en) * 1988-08-17 1992-03-31 Mitsubishi Kasei Corporation Porous glass and process for its production
US5120605A (en) * 1988-09-23 1992-06-09 Zuel Company, Inc. Anti-reflective glass surface
US5160358A (en) * 1989-03-31 1992-11-03 Mitsubishi Gas Chemical Co., Inc. Process for producing silica glass plate having controlled refractive index distribution
WO1993015422A1 (en) * 1992-01-29 1993-08-05 Lightpath Technologies, Inc. Refractive elements with graded properties and methods of making same
US5281303A (en) * 1991-09-27 1994-01-25 Corning Incorporated Process for manufacturing integrated optical components using silicon mask
US6136452A (en) * 1998-02-27 2000-10-24 The Regents Of The University Of California Centrifugal synthesis and processing of functionally graded materials
US20020157418A1 (en) * 2001-03-19 2002-10-31 Rahul Ganguli Process for reducing or eliminating bubble defects in sol-gel silica glass
US20040092396A1 (en) * 1999-04-08 2004-05-13 Affymetrix, Inc. Porous silica substrates for polymer synthesis and assays
US6929861B2 (en) 2002-03-05 2005-08-16 Zuel Company, Inc. Anti-reflective glass surface with improved cleanability
US20060019084A1 (en) * 2004-07-23 2006-01-26 Pearson Laurence T Monolithic composition and method
US20120105400A1 (en) * 2010-10-29 2012-05-03 Mathew Dinesh C Camera lens structures and display structures for electronic devices

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Publication number Priority date Publication date Assignee Title
JPS5792543A (en) * 1980-11-27 1982-06-09 Sumitomo Electric Ind Ltd Preparation of optical glass part

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US4302231A (en) * 1979-01-29 1981-11-24 Pedro Manoel Buarque De Macedo Method of producing a glass article having a graded refractive index profile of a parabolic nature
US4323381A (en) * 1979-01-19 1982-04-06 Hitachi, Ltd. Method for producing mother rods for optical fibers
US4436542A (en) * 1980-09-16 1984-03-13 Sumitomo Electric Industries, Ltd. Process for the production of an optical glass article

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US3597252A (en) * 1966-05-07 1971-08-03 Jenaer Glaswerk Schott & Gen Method for producing glass compositions
US3678144A (en) * 1970-06-12 1972-07-18 Corning Glass Works Silicate bodies containing coprecipitated oxides
US3821070A (en) * 1970-08-20 1974-06-28 Bayer Ag Producing novel silicon dioxide fibers
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US4178163A (en) * 1975-06-05 1979-12-11 Claus Wustefeld Method for the manufacture of foamed glass
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US4640699A (en) * 1982-05-14 1987-02-03 Hoya Corporation Process for producing glass product having gradient of refractive index
US4767435A (en) * 1984-02-14 1988-08-30 Hoya Corporation Process for producing transparent glass product having refractive index gradient
US4816049A (en) * 1985-07-12 1989-03-28 Hoya Corporation Process of surface treating laser glass
EP0215603A1 (en) * 1985-09-11 1987-03-25 AT&T Corp. Fabrication of high-silica glass article
US4872895A (en) * 1986-12-11 1989-10-10 American Telephone And Telegraph Company, At&T Bell Laboratories Method for fabricating articles which include high silica glass bodies
US4765818A (en) * 1987-02-24 1988-08-23 Hoechst Celanese Corporation Porous glass monoliths
US4898755A (en) * 1987-04-17 1990-02-06 Hoechst Celanese Corporation Inorganic-organic composite compositions exhibiting nonlinear optical response
US5100841A (en) * 1988-08-17 1992-03-31 Mitsubishi Kasei Corporation Porous glass and process for its production
EP0359588A2 (en) * 1988-09-16 1990-03-21 Hoechst Celanese Corporation Dye lasers
EP0359588A3 (en) * 1988-09-16 1990-08-16 Hoechst Celanese Corporation Dye lasers
US4944986A (en) * 1988-09-23 1990-07-31 Zuel Company Anti-reflective glass surface
US5120605A (en) * 1988-09-23 1992-06-09 Zuel Company, Inc. Anti-reflective glass surface
US5160358A (en) * 1989-03-31 1992-11-03 Mitsubishi Gas Chemical Co., Inc. Process for producing silica glass plate having controlled refractive index distribution
US5281303A (en) * 1991-09-27 1994-01-25 Corning Incorporated Process for manufacturing integrated optical components using silicon mask
WO1993015422A1 (en) * 1992-01-29 1993-08-05 Lightpath Technologies, Inc. Refractive elements with graded properties and methods of making same
US5262896A (en) * 1992-01-29 1993-11-16 Lightpath Technologies, L.P. Refractive elements with graded properties and methods of making same
US5582626A (en) * 1992-01-29 1996-12-10 Lightpath Technologies Limited Partnership Method for making refractive optical elements with graded properties
US6136452A (en) * 1998-02-27 2000-10-24 The Regents Of The University Of California Centrifugal synthesis and processing of functionally graded materials
US20040092396A1 (en) * 1999-04-08 2004-05-13 Affymetrix, Inc. Porous silica substrates for polymer synthesis and assays
US6824866B1 (en) 1999-04-08 2004-11-30 Affymetrix, Inc. Porous silica substrates for polymer synthesis and assays
US20020157418A1 (en) * 2001-03-19 2002-10-31 Rahul Ganguli Process for reducing or eliminating bubble defects in sol-gel silica glass
US6929861B2 (en) 2002-03-05 2005-08-16 Zuel Company, Inc. Anti-reflective glass surface with improved cleanability
US20060019084A1 (en) * 2004-07-23 2006-01-26 Pearson Laurence T Monolithic composition and method
US20120105400A1 (en) * 2010-10-29 2012-05-03 Mathew Dinesh C Camera lens structures and display structures for electronic devices
US9143668B2 (en) * 2010-10-29 2015-09-22 Apple Inc. Camera lens structures and display structures for electronic devices
US10009525B2 (en) 2010-10-29 2018-06-26 Apple Inc. Camera lens structures and display structures for electronic devices

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GB2084131A (en) 1982-04-07
JPS6121171B2 (ja) 1986-05-26
CA1158260A (en) 1983-12-06
DE3133541C2 (de) 1984-03-22
GB2084131B (en) 1984-04-18
JPS5742547A (en) 1982-03-10
DE3133541A1 (de) 1982-05-27

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